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Papers by Maksim Kulichenko
Structural characterization of the discrete [Sn@Cu12@Sn20]12− cluster exposed a fascinating archi... more Structural characterization of the discrete [Sn@Cu12@Sn20]12− cluster exposed a fascinating architecture composed of three concentric structural layers in which an endohedral Sn atom is enclosed in a Cu12 icosahedron, which in turn is embedded in an Sn20 dodecahedron. Herein, the possibility of sustaining aromatic behavior for this prototypical multilayered species was evaluated, in order to extend this concept to more complex clusters on the basis of magnetic response and bonding analysis by the AdNDP approach. This revealed characteristic features of spherical aromatics, given by the ability to sustain the shielding cone property, similar to archetypal aromatics.
In a high-resolution photoelectron imaging and theoretical study of the IrB3− cluster, two isomer... more In a high-resolution photoelectron imaging and theoretical study of the IrB3− cluster, two isomers were observed experimentally with electron affinities (EAs) of 1.3147(8) and 1.937(4) eV. Quantum calculations revealed two nearly degenerate isomers competing for the global minimum, both with a B3 ring coordinated with the Ir atom.
In this paper we suggest a new type of a single-atom (or single-defect) catalyst – MgO with perio... more In this paper we suggest a new type of a single-atom (or single-defect) catalyst – MgO with periodic defects on the (0 0 1) surface – which possesses noticeable non-linear optical properties. Periodicity of these defects leads to the significant extensive increase in the activity of a catalyst by growth of the concentration of active sites. In this work we showed the presence of diffuse electride-like multi-center bonds inside every periodic F-center. We also discovered that MgO with periodic defects on the surface gains non-linear optical properties due to electride-like polarizable bonds inside every defect. And most importantly, such defective structures are stable up to 1500 K opening wide range of applications even in extreme conditions.We considered both multiple (50% surface defects) and rare defects (12.5% surface defects) which are potential single-defect catalysts similar to ones that are referred as single-atom catalysts.
As is shown using the SSAdNDP approach, Mo and S form 2-centered bonds and there is a lone pair o... more As is shown using the SSAdNDP approach, Mo and S form 2-centered bonds and there is a lone pair on each S. Most importantly, the remaining electrons are distributed over Mo atoms and form conjugated aromatic σ-bonds inside every hexagonal ring, which makes molybdenum the main carrier of σ-aromaticity.
Chapter "14 - Spherical aromaticity in inorganic chemistry" in a book "Aromaticity... more Chapter "14 - Spherical aromaticity in inorganic chemistry" in a book "Aromaticity - Modern Computational Methods and Applications"
The Journal of Physical Chemistry, 2020
Molybdenum disulfide is a prominent semiconductor that received a lot of attention recently due t... more Molybdenum disulfide is a prominent semiconductor that received a lot of attention recently due to its unique properties. Possessing a layered crystal structure, one can tune the band gap from indirect to direct while transforming the material from the bulk to monolayer structure. MoS₂ is a highly researched material. However, not all of the nature of this intriguing material is revealed yet. The aim of this work is to deepen the knowledge of the scientific community about MoS₂ by deciphering its bonding picture. As is shown using the SSAdNDP approach, Mo and S form 2-centered bonds and there is a lone pair on each S. Most importantly, the remaining electrons are distributed over Mo atoms and form conjugated aromatic σ-bonds inside every hexagonal ring, which makes molybdenum the main carrier of σ-aromaticity.
In this paper, a new theoretically designed molecular species with electride characteristics is r... more In this paper, a new theoretically designed molecular species with electride characteristics is reported. The idea of this molecular electride comes from the formation of electride-like features in the MgO crystal with defect F-centers. The geometry of the investigated molecule can be described as a Mg4O4 cube with one oxygen atom removed.
The central unit of the synthesized structure is a Ru atom which is the vertex of the [RuPd2]+ tr... more The central unit of the synthesized structure is a Ru atom which is the vertex of the [RuPd2]+ triangle being the first example of mixed triangles among these metals. Moreover, Ru is involved in both σ- and π-aromaticity. σ-aromaticity is realized as the d-AO based multicenter bond which is delocalized over the inner [RuPd2]+ triangle with considerable contribution from the sulfur electron density. Besides, transition metals are known to interact with the electron cloud of benzene which, in turn, leads to the charge transfer and formation of conjugated electron density between the TM and benzene. The second type of aromaticity, π-aromaticity, is caused by this interaction and represented via d-AOs of Ru interacting with the benzene electron cloud. The doubly aromatic behavior is supported by MO and AdNDP (Adaptive Natural Density Partitioning) analyses. This doubly aromatic bonding pattern can also be described in terms of spiroaromaticity.
![Research paper thumbnail of “Bottled” spiro-doubly aromatic trinuclear [Pd2Ru]+ complexes](https://attachments.academia-assets.com/84761685/thumbnails/1.jpg)
](Chemical Science, 2021
Synthesis of a triangular [Pd2Ru]+ complex with delocalized metal–metal bonding between non-adjac... more Synthesis of a triangular [Pd2Ru]+ complex with delocalized metal–metal bonding between non-adjacent elements of the periodic table, double aromaticity and overlap of d-AOs with different angular momentum.
The Journal of Physical Chemistry A
The strong relativistic effects result in many interesting chemical and physical properties for g... more The strong relativistic effects result in many interesting chemical and physical properties for gold and gold compounds. One of the most surprising findings has been that small gold clusters prefer planar structures. Dopants can be used to tune the electronic and structural properties of gold nanoclusters. Here we report an experimental and theoretical investigation of a Zn-doped gold cluster, Au 9 Zn −. Photoelectron spectroscopy reveals that Au 9 Zn − is a highly stable electronic system with an electron binding energy of 4.27 eV. Quantum chemical studies show that the global minimum of Au 9 Zn − has a D 3h structure with a closed-shell electron configuration (1 A 1 '), which can be viewed as replacing the central Au atom by Zn in the open-shell parent Au 10 − cluster. The high electronic stability of Au 9 Zn − is corroborated by its extremely large HOMO−LUMO gap of 3.3 eV. Chemical bonding analyses revealed that the D 3h Au 9 Zn − are bonded by two sets of delocalized σ bonds, giving rise to double σ aromaticity and its remarkable stability. Two planar low-lying isomers are also observed, corresponding to a similar triangular structure with the Zn atom on the edge and another one with one of the corner Au atoms moved to the edge of the triangle.
The Journal of Physical Chemistry A
Because of its low toxicity, bismuth is considered to be a "green metal" and has receiv... more Because of its low toxicity, bismuth is considered to be a "green metal" and has received increasing attention in chemistry and materials science. To understand the chemical bonding of bismuth, here we report a joint experimental and theoretical study on a series of bismuth-doped boron clusters, BiBn- (n = 6-8). Well-resolved photoelectron spectra are obtained and are used to understand the structures and bonding of BiBn- in conjunction with theoretical calculations. Global minimum searches find that all three BiBn- clusters have planar structures with the Bi atom bonded to the edge of the planar Bn moiety via two Bi-B σ bonds as well as π bonding by the 6pz orbital. BiB6- is found to consist of a double-chain B6 with a terminal Bi atom. Both BiB7- and BiB8- are composed of a Bi atom bonded to the planar global minima of the B7- and B8- clusters. Chemical bonding analyses reveal that BiB6- is doubly antiaromatic, whereas BiB7- and BiB8- are doubly aromatic. In the neutral BiBn (n = 6-8) clusters, except BiB6 which has a planar structure similar to the anion, the global minima of both BiB7 and BiB8 are found to be half-sandwich-type structures due to the high stability of the doubly aromatic B73- and B82- molecular wheel ligands.
The Journal of Physical Chemistry Letters
Machine learning (ML) is quickly becoming a premier tool for modeling chemical processes and mate... more Machine learning (ML) is quickly becoming a premier tool for modeling chemical processes and materials. ML-based force fields, trained on large data sets of high-quality electron structure calculations, are particularly attractive due their unique combination of computational efficiency and physical accuracy. This Perspective summarizes some recent advances in the development of neural network-based interatomic potentials. Designing high-quality training data sets is crucial to overall model accuracy. One strategy is active learning, in which new data are automatically collected for atomic configurations that produce large ML uncertainties. Another strategy is to use the highest levels of quantum theory possible. Transfer learning allows training to a data set of mixed fidelity. A model initially trained to a large data set of density functional theory calculations can be significantly improved by retraining to a relatively small data set of expensive coupled cluster theory calculations. These advances are exemplified by applications to molecules and materials.
European Journal of Inorganic Chemistry
The Journal of Physical Chemistry C
![Research paper thumbnail of Correction: Can aromaticity be a kinetic trap? Example of mechanically interlocked aromatic [2-5]catenanes built from cyclo[18]carbon](https://attachments.academia-assets.com/67218920/thumbnails/1.jpg)
](Chemical Communications
Correction for ‘Can aromaticity be a kinetic trap? Example of mechanically interlocked aromatic [... more Correction for ‘Can aromaticity be a kinetic trap? Example of mechanically interlocked aromatic [2-5]catenanes built from cyclo[18]carbon’ by Nikita Fedik et al., Chem. Commun., 2020, 56, 2711–2714.
Chemical Communications
Aromaticity serves as a kinetic trap for mechanically interlocked cyclo[18]carbon rings.
The Journal of Physical Chemistry C
Structural characterization of the discrete [Sn@Cu12@Sn20]12− cluster exposed a fascinating archi... more Structural characterization of the discrete [Sn@Cu12@Sn20]12− cluster exposed a fascinating architecture composed of three concentric structural layers in which an endohedral Sn atom is enclosed in a Cu12 icosahedron, which in turn is embedded in an Sn20 dodecahedron. Herein, the possibility of sustaining aromatic behavior for this prototypical multilayered species was evaluated, in order to extend this concept to more complex clusters on the basis of magnetic response and bonding analysis by the AdNDP approach. This revealed characteristic features of spherical aromatics, given by the ability to sustain the shielding cone property, similar to archetypal aromatics.
In a high-resolution photoelectron imaging and theoretical study of the IrB3− cluster, two isomer... more In a high-resolution photoelectron imaging and theoretical study of the IrB3− cluster, two isomers were observed experimentally with electron affinities (EAs) of 1.3147(8) and 1.937(4) eV. Quantum calculations revealed two nearly degenerate isomers competing for the global minimum, both with a B3 ring coordinated with the Ir atom.
In this paper we suggest a new type of a single-atom (or single-defect) catalyst – MgO with perio... more In this paper we suggest a new type of a single-atom (or single-defect) catalyst – MgO with periodic defects on the (0 0 1) surface – which possesses noticeable non-linear optical properties. Periodicity of these defects leads to the significant extensive increase in the activity of a catalyst by growth of the concentration of active sites. In this work we showed the presence of diffuse electride-like multi-center bonds inside every periodic F-center. We also discovered that MgO with periodic defects on the surface gains non-linear optical properties due to electride-like polarizable bonds inside every defect. And most importantly, such defective structures are stable up to 1500 K opening wide range of applications even in extreme conditions.We considered both multiple (50% surface defects) and rare defects (12.5% surface defects) which are potential single-defect catalysts similar to ones that are referred as single-atom catalysts.
As is shown using the SSAdNDP approach, Mo and S form 2-centered bonds and there is a lone pair o... more As is shown using the SSAdNDP approach, Mo and S form 2-centered bonds and there is a lone pair on each S. Most importantly, the remaining electrons are distributed over Mo atoms and form conjugated aromatic σ-bonds inside every hexagonal ring, which makes molybdenum the main carrier of σ-aromaticity.
Chapter "14 - Spherical aromaticity in inorganic chemistry" in a book "Aromaticity... more Chapter "14 - Spherical aromaticity in inorganic chemistry" in a book "Aromaticity - Modern Computational Methods and Applications"
The Journal of Physical Chemistry, 2020
Molybdenum disulfide is a prominent semiconductor that received a lot of attention recently due t... more Molybdenum disulfide is a prominent semiconductor that received a lot of attention recently due to its unique properties. Possessing a layered crystal structure, one can tune the band gap from indirect to direct while transforming the material from the bulk to monolayer structure. MoS₂ is a highly researched material. However, not all of the nature of this intriguing material is revealed yet. The aim of this work is to deepen the knowledge of the scientific community about MoS₂ by deciphering its bonding picture. As is shown using the SSAdNDP approach, Mo and S form 2-centered bonds and there is a lone pair on each S. Most importantly, the remaining electrons are distributed over Mo atoms and form conjugated aromatic σ-bonds inside every hexagonal ring, which makes molybdenum the main carrier of σ-aromaticity.
In this paper, a new theoretically designed molecular species with electride characteristics is r... more In this paper, a new theoretically designed molecular species with electride characteristics is reported. The idea of this molecular electride comes from the formation of electride-like features in the MgO crystal with defect F-centers. The geometry of the investigated molecule can be described as a Mg4O4 cube with one oxygen atom removed.
The central unit of the synthesized structure is a Ru atom which is the vertex of the [RuPd2]+ tr... more The central unit of the synthesized structure is a Ru atom which is the vertex of the [RuPd2]+ triangle being the first example of mixed triangles among these metals. Moreover, Ru is involved in both σ- and π-aromaticity. σ-aromaticity is realized as the d-AO based multicenter bond which is delocalized over the inner [RuPd2]+ triangle with considerable contribution from the sulfur electron density. Besides, transition metals are known to interact with the electron cloud of benzene which, in turn, leads to the charge transfer and formation of conjugated electron density between the TM and benzene. The second type of aromaticity, π-aromaticity, is caused by this interaction and represented via d-AOs of Ru interacting with the benzene electron cloud. The doubly aromatic behavior is supported by MO and AdNDP (Adaptive Natural Density Partitioning) analyses. This doubly aromatic bonding pattern can also be described in terms of spiroaromaticity.
Chemical Science, 2021
Synthesis of a triangular [Pd2Ru]+ complex with delocalized metal–metal bonding between non-adjac... more Synthesis of a triangular [Pd2Ru]+ complex with delocalized metal–metal bonding between non-adjacent elements of the periodic table, double aromaticity and overlap of d-AOs with different angular momentum.
The Journal of Physical Chemistry A
The strong relativistic effects result in many interesting chemical and physical properties for g... more The strong relativistic effects result in many interesting chemical and physical properties for gold and gold compounds. One of the most surprising findings has been that small gold clusters prefer planar structures. Dopants can be used to tune the electronic and structural properties of gold nanoclusters. Here we report an experimental and theoretical investigation of a Zn-doped gold cluster, Au 9 Zn −. Photoelectron spectroscopy reveals that Au 9 Zn − is a highly stable electronic system with an electron binding energy of 4.27 eV. Quantum chemical studies show that the global minimum of Au 9 Zn − has a D 3h structure with a closed-shell electron configuration (1 A 1 '), which can be viewed as replacing the central Au atom by Zn in the open-shell parent Au 10 − cluster. The high electronic stability of Au 9 Zn − is corroborated by its extremely large HOMO−LUMO gap of 3.3 eV. Chemical bonding analyses revealed that the D 3h Au 9 Zn − are bonded by two sets of delocalized σ bonds, giving rise to double σ aromaticity and its remarkable stability. Two planar low-lying isomers are also observed, corresponding to a similar triangular structure with the Zn atom on the edge and another one with one of the corner Au atoms moved to the edge of the triangle.
The Journal of Physical Chemistry A
Because of its low toxicity, bismuth is considered to be a "green metal" and has receiv... more Because of its low toxicity, bismuth is considered to be a "green metal" and has received increasing attention in chemistry and materials science. To understand the chemical bonding of bismuth, here we report a joint experimental and theoretical study on a series of bismuth-doped boron clusters, BiBn- (n = 6-8). Well-resolved photoelectron spectra are obtained and are used to understand the structures and bonding of BiBn- in conjunction with theoretical calculations. Global minimum searches find that all three BiBn- clusters have planar structures with the Bi atom bonded to the edge of the planar Bn moiety via two Bi-B σ bonds as well as π bonding by the 6pz orbital. BiB6- is found to consist of a double-chain B6 with a terminal Bi atom. Both BiB7- and BiB8- are composed of a Bi atom bonded to the planar global minima of the B7- and B8- clusters. Chemical bonding analyses reveal that BiB6- is doubly antiaromatic, whereas BiB7- and BiB8- are doubly aromatic. In the neutral BiBn (n = 6-8) clusters, except BiB6 which has a planar structure similar to the anion, the global minima of both BiB7 and BiB8 are found to be half-sandwich-type structures due to the high stability of the doubly aromatic B73- and B82- molecular wheel ligands.
The Journal of Physical Chemistry Letters
Machine learning (ML) is quickly becoming a premier tool for modeling chemical processes and mate... more Machine learning (ML) is quickly becoming a premier tool for modeling chemical processes and materials. ML-based force fields, trained on large data sets of high-quality electron structure calculations, are particularly attractive due their unique combination of computational efficiency and physical accuracy. This Perspective summarizes some recent advances in the development of neural network-based interatomic potentials. Designing high-quality training data sets is crucial to overall model accuracy. One strategy is active learning, in which new data are automatically collected for atomic configurations that produce large ML uncertainties. Another strategy is to use the highest levels of quantum theory possible. Transfer learning allows training to a data set of mixed fidelity. A model initially trained to a large data set of density functional theory calculations can be significantly improved by retraining to a relatively small data set of expensive coupled cluster theory calculations. These advances are exemplified by applications to molecules and materials.
European Journal of Inorganic Chemistry
The Journal of Physical Chemistry C
Chemical Communications
Correction for ‘Can aromaticity be a kinetic trap? Example of mechanically interlocked aromatic [... more Correction for ‘Can aromaticity be a kinetic trap? Example of mechanically interlocked aromatic [2-5]catenanes built from cyclo[18]carbon’ by Nikita Fedik et al., Chem. Commun., 2020, 56, 2711–2714.
Chemical Communications
Aromaticity serves as a kinetic trap for mechanically interlocked cyclo[18]carbon rings.
The Journal of Physical Chemistry C